Process of making fatty acids.



UNITED STATES Patented June '7, 190 1.

PATENT OFFICE.

IVILHELM OONNSTEIN, OF OI-IARLOTTENBURG, GERMANY, ASSIGNOR TO VEREINIGTEGHEMISCHE IVERKE ACTIEN-GESELLSCHAFT, F CHAR- LOTTENBURG, GERMANY, AFIRM.

PROCESS OF MAKING FATTY ACIDS.

SPECIFICATION forming part of Letters Patent No. 762,026, dated June 7,1904.

' Application filed October 24, 1902. Serial No. 128,657. (Nospecimens.)

To all whom it may concern:

Be it known that I, I/VILI-IELM CoNNsTEIN, doctor of medicine, a subjectof the King of Prussia, German Emperor, residing at 16 Salzufer,Charlottenburg, Kingdom of Prussia, German Empire, have invented new anduseful Improvements in Processes for the Manufacture of the Fatty Acidsfrom Their Esters, of which the following is a specification.

This invention relates to the process of manufacturing fatty acids fromtheir esters and materials containing the said esters by means offerments, and has for its object to 5 render the process moreexpeditious and considerably cheaper.

The presence of fat-decomposing ferments in'oil-bearing seeds of plantshas been observed by Green (Proceedings 0 f the Royal S0- 2 0 cz'etySeptember 20, 1890, Green-Windisch Die Emg me, Berlin, 1901, page 230)and by Sigmund (iYmcts/Lefte filr Chem/dc, 1890, page 268, and Reportsof 1I[cctings 0f the Vieamc Academy of Sciences for July 1, 1891) in the5 course of their inquiries instituted with the view of ascertainingcertain questions relating to the physiology of plants. These authorshave established it as a fact that during the process of trituration ofoleaginous seeds with 3 water there gradually forms acid, and theyexplained this circumstance by the existence in the seeds of a fermentwhich had the property of decomposing the fats also contained in theseed into free. fatty acid-for instance, palmitic, stearic, oleicacid-and glycerin. They state, however, that the ferment becomesinoperative owing to the presence of small quantities of alkali or acid.They also point out that if the operations be conducted under 4 theconditions and within the limits which they have laid down thedecomposition will progress up to a certain stage only, and this amountsto saying that when their conditions are adhered to the decomposition ofthe fattyacid esters is not possible by this process for industrial ortrade purposesthat is, on a somewhat large scale.

Now I have found that the decomposition of the fats can be renderedpossible and available for purposes of manufacture on a large'scale bymeans of the ferments contained in many plants and in particular in theEuplam-bz'cceee, more especially the Rz'cinas (castor-oil) varieties ofthat order of plants, by diverging from the methods communicated byGreen and Sigmund in this, that instead of causing the ferments toexercise their action in a neutral solution this action is induced in anacid solution, by which modified mode of procedure not only are theesters decomposed nearly quantitatively, but improved results are,moreover, attained in the following direction.

In an acid solution it is principally the more important higherfatty-acid esters which are attacked, whereas if the conditions statedby Green and Sigmund be maintained all that becomes decomposed are theesters of the lower fatty acids containing a smaller number of atoms ofcarbon which are of less technical importance.

The utilization of the observations above mentioned in the decompositionof fatty-acid esters for industrial purposes may take place by causingthe ferments of the plants to act upon the fats to be decomposed inpresence of a certain amount of acid, such as sulfuric acid, added atthe beginning of the operation.

The conditions which should be complied with in order to insure the bestpossible results are the following: First, the maintenance of not toohigh a temperaturc-say between 10 and LO centigrade-and,second, thepresence of small amounts of acids in a diluted state. This method ofoperation has proved particularly effective in the case of sulfuric acidconcentrated toa density of onetenth normal standard and of hydrochloricacid, although it is applicable also to organic acids. The organic acidmight be either added to the fat under treatment artificially at thebeginning of the operation or may be allowed to develop of its ownaccord in the course of the process of decomposition. When the fat isprepared for treatment without an immediate addition of acid, theregradually takes place a slight splitting of the lowgraded fatty-acidesters; but it will not be until after several days that a quantity ofacid will become free sufiicient to initiate an energetic decompositionof the fatty-acid esters of a higher order.

An example may serve to explain the facts described. Upon trituratingfive grams of shelled ricinus-seed with cold water acid equal to 1.2cubic centimeters of a one-tenth normal solution of soda-lye will befound to have formed after an interval not exceeding about half an hour.After two days standing the proportion of acid will be found to havedoubled (2.5 cubic centimeters one tenth normal NaOH) and eventually, bythe time that four days have elapsed, the acid which has been slowlyincreasing in quantity will have reacheda sufficiently high degree ofconcentration to initiate a powerful and energetic decomposition of thefatty-acid esters of higher order/I. 6., containing a relatively highnumber of carbon atoms-with the result that now, on the fourth day, theproportion of acid has suddenly rushed up to fifty-nine cubiccentimeters one-tenth normal NaOI-I. Instead of in four days this resultmight have been obtained within a few hours had a certain amount ofone-tenth normal sulfuric acid been added to the ricinus-seed and wateremulsion from the first.

Green and Sigmund in their experiments had arrived at the unsatisfactoryresults which they report because they were under the mistakenimpression that acid would impair the ferment and because they woulddiscontinue operations at a period at which no energetic action couldpossibly have set in from lack of aeid.-

Further conditions to be observed are-- Third. The presence of an amountof water at least equal to the theoretical quantity found by thefollowing general equation:

RCOOR1+ H2O I RCOOH-l- R1OH.

For instance:

Palmitic glycerin e: er

C11;I I32O2+ H):;

Palmitic Glycerin acid Fourth. hat is of especial importance in carryingout this process is that the fats should be present in a state ofemulsion. The emulsion may be prepared in any known manner for producingfrom fats, oils, &c.* for example, by triturating the fat to bedecomposed together with the constituent parts of the plants and withwater.

If the above conditions be complied with, an adequate result may befully relied on. Thus by treating together six kilograms ofricinus-seed, one hundred kilograms of tallow, palm-oil, blubber,(train-0H,) or other fats, twenty kilograms of water, and one hundredgrams of concentrated sulfuric acid, mixing the whole until an emulsionis produced and allowing the emulsion to stand at rest, there will beobtained as a result an approximately quantitative splitting up ordecomposition of the neutral fat. The products of such decomposition(the fatty acids of the respective fats or oils and glycerin) separatedby the usual methodssuch as pressing, filtering, &c.are of so high adegree of purity that an equivalent could otherwise be obtained only byresorting to uncommonly expensive processes of purification.

An instance of the employment of the process for the manufacture offatty acids from fats of animal origin and as showing its practicabilityfor use with all fats and oils, whether they be fatty-acid esters ofglycerin or others, may be given as follows: Fifteen kilograms ofspermaceti (VValrat) are triturated with 4.5 kilograms of ricinus-seedand 7L ten kilograms 17) of acetic acid and maintained for a period ofeighteen hours at a temperature of 35 After this period thirty two percent. of the spermaceti will be split off into the fatty acid.

Now it has been found that the addition of acids is not absolutelynecessary in carrying out this process, but may be replaced generally bytreatment calculated to bring about an acid reaction. The essentialcondition whereon the success of the process depends is that theferments should operate in a me dium capable of acid reaction, While itis not an indispensable condition that such acid reaction should beinduced by the presence of free acids.

In accordance with this process the novel observation is taken advantageof by causing the ferments to act upon the emulsion of the fats inpresence of acid salts-e. g., sodium bisulfate, acid sodium phosphate,or the like. In other respects the performance of the process is thesame as if acid were employed in accordance with the foregoingdescription.

The acid salts may be superadded in solutions; but an addition may takeplace also in a solid form, so that the solution shall be produced onlygradually. The degree of concentration is preferably one-tenth normal.

What I claim as my invention, and desire to secure by Letters Patent,is*

1. The process of decomposing fatty-acid esters into their acids andalcohols, which con= sists in providing a medium of acid reaction,emulsifying said esters to be treated and subjecting said emulsion inthe presence of the said medium of acid reaction to the action of thefat-decomposing ferments present in oil or fat bearing plants,

2. The process of decomposing fatty-acid In Witness whereof I havehereunto signed esters into their acids and alcohols,wh1ch conmy name,this 8th day of October, 1902, in the sists in providing a medlumcontaining free presence of two subscribing Witnesses.

acid, emulsifying the esters to be treated and WILHELM CONNSTEIN. 5subjecting said emulsion in the presence of Witnesses:

said free acid to the action of the fat-decom- WOLDEMAR HAUPT,

posing ferments present in ricinus-seed. HENRY HASPER.

